Polymer composition comprising a resinous polymer and the salt obtained by reacting a quaternary ammonium compound with an anionic surface active compound and method of making same



description proceeds.

POLYMER coMrosrrroNfcoMrnlsrNo A RESIN- This 'iiiven'tion relates to newand valuable plastic compositions'and more particularly to plasticcomposi tions comprising 'hi'gh polymer, non-rubber plasticmaterial'fand to a process of compounding such plastic material. I i dIt is one object of the present invention'to considerably facilitateworking and compounding of high polymer nonrubber plastic materials with"solid, pulverulent additives,

such as fillers, loading agents, pigments,'an'd the like and to readily,homogeneously, and intimately, incorporate such additives into andevenly distribute the same throughout said'lii'ghpolymer non-rubberplastics.

Another, object of the resent invention is to pr u'litle new andvaluable plastic compositions of considerably improved mechanicalstrength properties. e

Other objects of the present invention and advantageous features thereofwill become apparent as the In principle, the process according to theprese t inv United States Patent "we 4 2,925,397 w Fe -'1? or otherpulverulent compounds can also be added. to impart specific andcharacteristic properties to the resulting compositions. The resultingcompositions'ar'e further worked up' in the conventional manner and canbe converted, for instance, into filaments, films, foils, sheets,blocks, or otherwise shaped products, I

' For producing organic electroneutral salts for the purpose ofthepresent invention, known cationic surfaceactive onium compounds areused, such as, 'for instance, organic ammonium, sulfonium, phosphonium,and the like compounds. "Said oniuin compounds, preferably,

contain at least one aliphatic, cycloaliphatic, aliphatic-, I aromatic,or cycloaliphatic-aromatic residue with at least 6 carbon atoms.Said-residue ;may contain upto 20 and even more carbon atoms. Thehydrocarbon radicals of said compounds may also contain hetero "atoms,or grou s of hetero atoms, or suitable s'ubs'titu'tents.

' The known organic ammonium compounds derived from ammonia or fromorganic nitrogen bases are of particular practical interest. Suchcompounds are, for

, instance, 'trirnethylv 'oc'tyl amoni'um chloride, trime'th'yl yentionfor working up andcomp'oundin'g high polymer compositions ischaracteriaed by the incorporation into said plastic compositions oforganic electric-neutral salts as they are obtained by reactingequimole'cular amounts of anionic surface-active and cationicsurfaee-ac'tive compound-s. U

.High polymer non-rubber plastic materials as they are employedaccording to the present invention are, for

example, the well known polyvinyl compoundsfs'u'ch as polyvinylchloride, polyvinyl acetate, polyacrylic; acid compounds, such aspolyacrylonitrile, polyacrylic acid esters, polymethacrylic acid esters,polystyrenes', polyarnides, 'such as the polyamides from hexamethylenediamine and adipic acid, polyesters, such "a's'iphthalic' acidglycerides, cellulose derivatives, such asfcellulosenit-rates, celluloseacetates, cellulose acetate bmym es, and the like. However, rubbercompounds such; as naturalrubher, various typesof synthetic 'rubber, orreclaimed rubher are excluded from thisapplication but are included inapplication Serial No. 435,358, filed June 8, 195 4...

As a result of the addition of such organic electroneutral salts,working up and compounding of said high polymer non-rubber plastics isconsiderably facilitated. More particularly incorporation of solidpulverulent additives, such as fillers, loading agents, pigments and thelike, isconsiderably.improved since saidadditives are rapidly wettedwith and are very intimately and homogeneously distributed throughoutsaid plastics.

Furthermore, said electro-neut'ral salts as such orin combination withknown plasticizers and gelatinizing -=hydroxides,qor salts, finely'dispersed silicaftalc, kaolin,

dodecyl ammonium chloride, trirnethyl octadecyl amrnOniurri rr'iethosulfate, dimethyl dioctade'cyl ammonium chloride,ditnethyl'dod'ecyl benzyl amonium chloride, dimethyl cyclohexyl alkylammonium chlorides with 10 to 22 carbon atoms in their alkyl radical, ormixtures of such corn-pounds, 'dodecyl pyridinium chloride, hexadecylpyridinium bisul-fate, and the like. As stated above, the alkyl radicalsin said ammonium compounds may alsocontain hetero atoi'ns such asoxygen, sulfur, or nitrogen, or groups of hetero atoms derivedtherefrom, or suitable substitutents.

Anionic surface-active compounds which can be used as theother' reactioncomponent in the production of the required 'or'g'anic electro neut'ralsalts, are, preferably, known compounds of the aliphatic,cycloaliphatic, aliphaticaromatic, or cycloaliphat'ic-aromatic serieswhich h'ave'in their molecule at least one residue with at least sixcarbon atoms and up to twenty 'and' even more carbon atoms and at leastone acid, s'alt-forrriing group, wherein said acid, salt-forming groupis neutralized-by an inorganic or organic base capable of forming awater soluble salt with said compound. Compounds of this type are,- forinstance, alkyl sulfates, alkyl sulfon'ates, alkyl benzene sulfonates,salts of. sulfonat'ed oils and fats, salts of dialkyl or di-alkylaryl-disulfonic acid imides,or of dialkyl or di-alkyl-aryl-sulfoniccarboxylic acidimides, salts of fatty acids or of resin acids, salts ofcondensation products of higher molecular carboxylic acid halogenidesor-of higher molecular 'sulfonic acid 'halogenides with proteins and thelike. vThe hydrocarbon radicals of said compounds can also beinterrupted by hetero atoms, such as oxygen, sulfur, or nitrogen, or bygroups of hetero atoms, such as, for instance, tester, carboxylic acidamide, or sulfonic acid amide groups and the like. ,Said radicals mayalso contain suitable substituents such as hydroxyl, mercapto, aminogroups or the like. I Other anionic surface-active compounds which maybe employed as the other reaction component in the production of therequired electro-neutral salts are, forinstance, water soluble salts ofhigher molecular fatty acids with at least six carbon atoms, wax acids,naphthenic acids, resin acids, oct'yloxy acetic acid, 'hexadecylmercapto acetic acid, .C.-alkyl cresoxy acetic acid, salts of compoundscontaining inorganic acid groups, such as'dodec'yl sulfuric acid ester,the sulfuric acid ester mixture of a mixture of aliphatic alcoholsobtained by catalytic reduction'of coconut oil, oleyl sulfuricacidester, the sulfuricacid ester of ethyIene 'glycoI inonoocty'l ether, themono-or disulfur'ic acid ester of glycerol mono'stearic acid er,

the phosphoric acid ester of- 'de'canediol-monoacetate, the

w-butyl ether of decyl sulfuric acid ester, the w-hexyl thioether ofoctyl thiosulfuric acid ester, N-butyl-N- doecyl sulfamic acid, thesulfuric acid ester of B-hydroxy- 'y-(secondary octyl cresoxy) propane,secondary octyl phenoxy ethane sulfuric acid ester, N-oleoyl-N-methylamino ethane-B-sulfonic acid, stearoyloxy ethane-[3- sulfonic acid,N-cetyl sulfonic sulfanilic acid, the w-cyclohexyl ether of decanesulfonic acid, secondary octyl phenyl benzyl ether-4'-sulfonic acid,salts of alkyl benzene sulfonic acids the alkyl thereof having betweenabout six and about 18 carbon atoms, of the mixture of isomeric2-isoalkyl cresoxy benzoic acid sulfonic acids-5, the alkyl radicalthereof having 5 to 11 carbon atoms, of l-secoudary octyl phenoxybenzene-2,5-disulfonic acid, of l-secondary hexyl phenoxy-Z-(acetylamino) benzene- 4-sulfonic acid, of the sulfonation product of thesecondary octyl-l-cresyl benzyl ether, of the sulfonation product of'cresoxy acetic acid dodecylamide, and others.

The electro-neutral salts used according to the present invention areprepared from said starting materials for instance, by mixingequimolecular amounts of an aqueous solution of the anionicsurface-active component with an aqueous solution of the cationicsurface-active component whereby the electro-neutral salt precipitates.It is understood, of course, that the hydrocarbon radicals of bothcomponents may be alike or different from each other.

The resulting precipitated products can directly be used for the purposeof this invention or they are first purified, freed from their saltcontent, and dried. Under certain conditions it is possible to use, inplace of said electro-neutral salts, equimolecular amounts of theirstarting components.

Said organic electro-neutral salts can be incorporated as such into theplastic composition or in the form of their aqueous solutions ordispersions, or in form of solutions in organic solvents. The amounts tobe incorporated vary according to the purpose for which said plasticcompositions are employed and are between about 0.2% and about 30.0% andeven more, calculated for the amount of polymer present in said plasticcomposition. Ordinarily, amounts between about 3% and about 20% yieldfully satisfactory results.

The following examples serve to illustrate the present inventionwithout, however, limiting the same thereto.

Example I '90 parts by weight of a mixed polymerization product of vinylchloride and vinyl acetate are compounded, by means of heated rollers,with 15 parts by weight of an organic electro-neutral salt prepared byreacting equivalent amounts of dimethyl octyl cyclohexyl ammoniumchloride and the sodium salt of capric acid (C H C0ONa), and with 30parts by weight of the penta-erythritol ester of the first runnings offatty. acids having 4 to 6 carbon atoms. The resulting composition iscalendered into foils of excellent elasticity and cold resistance.

Example ll 75 parts by weight of a polyamide made from hexamethylenediamine and adipic acid are melted and are mixed in said molten statewith 20 parts by weight of the organic electro-neutral salt prepared byreacting equimolecular amounts of tri-methyl octyl ammonium chloride andthe sodium salt of capric acid. The molten composition, on extrudingthrough nozzles, yields clear, elastic foils.

In a similar manner other organic electro-neutral salts as they areobtained by reacting equimolecular amounts of cationic surface-activecompounds and anionic surfaceactive compounds, such as namedhereinbefore, can be incorporated into and compounded with high polymernon-rubber plastic materials. In place of heated rollers,

and e pecially where dispersion of pigments and the like 4 is notnecessary, heavy kneaders may be used. Ball mills also find a largescale application, for instance, when incorporating pigments in plasticcompositions of such polymer non-rubber plastic materials.

Various other methods of preparing said organic electro-neutral saltsare described in said co-pending application Serial No. 435,358, filedJune 8, 1954, and salts prepared according to said application may alsobe used according to the principles of this invention, also variousmodifications and changes may be made from the embodiments describedherein within the principles of this invention and the scope of thefollowing claims.

We claim:

1. A solid high polymer plastic composition inwhich additives can beeasily and intimately dispersed which plastic composition consistsessentially of a plastic selected from the group consisting of polyvinylhalides, polyvinyl acetate, polyacrylonitrile, polystyrene, polyamide ofhexamethylene diamine and adipic acid and polyester of glycerol andphthalic acid having incorporated therein and intimately and thoroughlydispersed therethrough "a water-insoluble organic salt precipitateobtained by adding together an aqueous solution of organic cationicsurfacein an amount between about 3% and about 20% of the amount of saidplastic present in said solid high polymer plastic composition.

.2. A solid high polymer plastic composition in which additives can beeasily and intimately dispersed which consists essentially of apolyamide of hexamethyleue diamine and adipic acid having incorporatedtherein and intimately and thoroughly dispersed therethrough a.water-insoluble organic salt precipitate obtained by reactingequimolecular amounts of an aqueous solution of atri-lower-alkyl-mono-higher-alkyl ammonium halide with an aqueoussolution of an alkali metal salt of a fatty acid containing 6 to 20carbon atoms in an amount between about 3% and about 20% of the amountof said polyamide.

3. A method of producing a high polymer plastic composition into whichadditives can be easily and intimately dispersed which consists inmechanically mixing a solid plastic selected from the group consistingof polyvinyl halides, polyvinyl acetate, polyacrylonitrile, polystyrene,polyamide of hexamethylene diamine and adipic acid and polyesters ofglycerol and phthalic acid with from about 3 to about 20% based on theweight of the solid plastic of a water-insoluble organic saltprecipitate obtained by adding together an aqueous solution of organiccationic surface-active quaternary ammonium compounds having at leastone aliphatic hydrocarbon radical containing 6 to 22 carbon atoms and anaqueous solution of an organic anionic surface-active compound having atleast one aliphatic hydrocarbon radical containing 6 to 20 carbonconsists essentially of a mixed polymerization product of ReferencesCited in the'file of this patent vinyl chloride and vinyl acetate havingincorporated there- UNITED STATES PATENTS in and intimately andthoroughly dispersed therethrough a water-insoluble organic saltprecipitate obtained by re- 22,76,305 Hershberger "f'" 1942 actingequimolecular amounts of an aqueous solution of 5 23131154 Kelly et 1943dimethyl-octyl-cyclohexyl ammonium chloride with an 2360'990 vanValkenburgh -r- 1944 aqueous solution of the sodium salt of a capricacid in 2'373173 Dean 1945 an amount of 16.7% of the amount of saidpolyamide. 2'413197 Smith et 24,1946

1. A SOLID HIGH POLYMER PLASTIC COMPOSITION IN WHICH ADDITIVES CAN BEEASILY INTIMATELY DISPERSED WHICH PLASTIC COMPOSITION CONSISTSESSENTIALLY OF A PLASTIC SELECTED FROM THE GROUP CONSISTING OF POLYVINYLHALIDES, PLOYVINYL ACETATE, POLYACRYLONITRILE, POLYSTYRENE, POLYAMIDE OFHEXAMETHYLENE DIAMINE AND ADIPIC ACID AND POLYESTER OF GLYCEROL ANDPHTHALIC ACID HAVING INCORPORATED THEREIN AND INTIMATELY AND THOROUGHLYDISPERSED THERETHROUGH A WATER-INSOLUBLE ORGANIC SALT PRECIPITATEOBTAINED BY ADDING TOGETHER AN AQUEOUS SOLUTION OF ORGANIC ANIONICACTIVE QUANTERNARY AMMONIUM COMPOUNDS HAVING AT LEAST ONE ALIPHATICHYDROCARBON RADICAL CONTAINING 6 TO 22 CARBON ATOMS AND AN AQUEOUSSOLUTION OF AN ORGANIC ANIONIC SURFACE-ACTIVE COMPOUND HAVING AT LEASTONE ALIPHATIC HYDROCARBON RADICAL CONTAINING 6 TO 20 CARBON ATOMS AND ATLEAST ONE ACID RADICAL CAPABLE OF BEING NEUTRALIZED BY AN ORGANIC BASETO FORM A SALT THEREWITH SELECTED FROM THE GROUP CONSISTING OF SULFURICACID RADICALS, SULFONIC ACID RADICALS, PHOSPHORIC ACID RADICALS ANDCARBOXYLIC ACID RADICALS, SAID CATIONIC AND SAID ANIONIC COMPOUNDS BEINGIN SUBSTANTIALLY EQUIMOLAR PROPORTIONS IN SAID PRECIPITATE, AMOUNTBETWEEN ABOUT 3% AND ABOUT 20% OF THE AMOUNT OF SAID PLASTIC PRESENT INSAID SOLID HIGH POLYMER PLASTIC COMPOSITION.